Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
  • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
  • C07C29/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
  • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
  • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
  • C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0025—Foam properties rigid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2115/00—Oligomerisation
  • C08G2115/06—Oligomerisation to carbodiimide or uretone-imine groups
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
  • Y10S264/05—Use of one or more blowing agents together
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S521/901—Cellular polymer containing a carbodiimide structure
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S521/903—Cellular polymer having reduced smoke or gas generation

Definitions

• the foam compositions of the present invention are rigid cellular plastics which are suitable replacements for the heretofore known foams in many applications such as insulating material and the like.
• the foam compositions of the present invention exhibit excellent flame retardancy and low smoke densities.
• the present invention provides novel rigid foam compositions which are prepared from the catalytic condensation of an organic polyisocyanate in the presence of a 2,4,6-tris(dialkanolamino )-s triazine catalyst. It appears that the foam forming reaction of the present invention proceeds in accordance with the following equation:
• R and R are each polyvalent organic radicals which may be the same or different.
• the evolution of carbon dioxide by the reaction provides a sufficient blowing agent for inducing and promoting foam formation.
• one readily apparent advantage of the present invention is seen to be the elimination of the need for the addition of any blowing agents to the reaction.
• the reaction is exothermic and the heat generated therefrom also promotes foam formation. But it is the self-evolution of carbon dioxide which is essential in the formation of the foams of the present invention.
• R is a polyvalent organic radical selected from the group of aliphatic, aromatic and alkylaryl organic radicals.
• O is oxygen and z is an integer corresponding to the valence number of R and is at least 2.
• Representative organic polyisocyanates contemplated herein include, for example, the aromatic diisocyanates, such as: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene diphenyl diisocyanate; the aromatic triisocyanates such as 3,3,3"-triphenylmethane triisocyanate; the aromatic tetraisocyanates and the like; alkylaryl polyisocyanates such as xylylene diisocyanates; aliphatic polyisocyanates such as lysine diisocyanate methyl ester and the like, and mixtures thereof.
• polyisocyanates are prepared by conventional methods known in the art such as the phosgenation of the corresponding organic amine.
• Still another class of organic polyisocyanates contemplated by the present invention are the so-called quasi-prepolymers. These are prepared by reacting an excess of any of the above-enumerated organic polyisocyanates or mixtures thereof with a minor amount of an organic polyol.
• These polyols which can be either polyether polyols or polyester polyols, and their methods of preparation are Well known in the art. The use of any one specific polyol is not critical hereto, rather any polyol that can be used to prepare a quasi-prepolymer can be employed herein.
• the quasi-prepolymers are prepared by reacting an organic polyisocyanate with a minor amount, usually about to 15% by weight, based on the weight of the polyisocyanate, of the polyol.
• a minor amount usually about to 15% by weight, based on the weight of the polyisocyanate, of the polyol.
• the specific catalyst employed in the present invention, as hereinbefore noted, consists of a 2,4,6-tris(dialkanolamino)-s-triazine.
• the catalyst include 2,4,6-tris-(diethanolamino)-s-triazine, 2,4,6-tris(diisopropanolamino) -striazine; 2,4,6-tris (dibutanolamino) s-triazine and the like as well as mixtures thereof.
• any of the homologues of 2,4,6-tris,(diethanolamino)-striazine exhibit utility in the present invention. It is preferred, however, to employ 2,4,6-tris(diethanolamino)-striazine.
• Preparation of these triazine catalysts generally comprises condensing cyanuric chloride with the selected dialkanol amine in the presence of a neutralizing amount of sodium hydroxide.
• 2,4,6-tris-(diethanolamino)-s-triazine is prepared from the condensation of diethanolamine and cyanuric chloride in the presence of a neutralizing amount of sodium hydroxide.
• the triazine compounds and their methods of preparation are more fully described by Kaiser et al. Journal of the American Chemical Society, v. 73, p. 2984 (1951).
• a catalytic amount of the triazine catalyst consists of from about 0.1 to parts by weight of the catalyst, based on 100 parts by weight of the polyisocyanate. Preferably, from about 0.5 to 3.0 parts by weight of catalyst based on 100 parts by weight of polyisocyanate is employed herein.
• the foam compositions of the present invention are prepared by gradually heating the organic polyisocyanate in the presence of the catalyst at a temperature ranging from about 70 C. to 200 C.
• the reaction is conducted over a temperature gradient ranging from about 80 C. to 120 C.
• the reaction can be carried out at atmospheric, superatmospheric or subatmospheric pressures, it ispreferred to employ atmospheric pressures.
• reaction is exothermic. This exotherm is evidenced by an increase in temperature in the reaction environment as well as being accompanied by foam formation.
• the gradual heating of polyisocyanate reagent is conducted over a period of from about 3 to 120 minutes and usually from about 5 to 60 minutes, after which time the exotherm becomes evident.
• the required time to complete the reaction is, of course, dependent on the type of polyisocyanate and amount of catalyst employed.
• Various other ingredients can be incorporated into the rigid foams of the present invention to enhance the properties thereof.
• minor amounts of active ingredients such as organic polyols can be employed. Generally from about 1 to 20 parts by weight of polyol per 100 parts by weight of polyisocyanate can be used herein.
• various surfactants, plasticizers and filler materials can also be employed herein in amounts ranging from 1 to parts by weight of each per 100 parts by weight of polyisocyanate.
• the organic polyols that can be used as a separate ingredient are the same as those used in the formation of the above-mentioned quasi-prepolymer.
• the polyhydric alcohols the polyether polyols prepared by oxyalkylating polyhydric alcohols; polyester polyols prepared from the reaction of a polycarboxylic acid and a polyhydric alcohol; the oxyalkylation adducts of the polyester polyols; various phosphorous containing polyols and the like.
• the mercapto-compounds such as dithiols and the like.
• surfactants are the well-known silicon-based polysiloxane surfactants.
• Filler materials such as calicum carbonate, barium sulfate, calcium oxide and the like can be employed in the foam preparation.
• plasticizers such as tris(betachloroethyl) phosphate. and dioctyl phthalate are contemplated for use herein.
• the final foam products obtained by the practice of the present invention generally have densities ranging from about 0.5 to 20.0 lbs/cu. ft. and usually from about 0.8 to 16.0 lbs/cu. ft.
• EXAMPLE 1 This example illustrates the preparation of a carbodiimide foam composition in accordance with the present invention.
• the mixture was maintained at a temperature of about 100 C. and under constant, slow stirring. After about 30 minutes an exotherm occurred which was accompanied with the evolution of carbon dioxide and foam formation. The peak temperature reached by the exotherm was 181 C. After about 60' minutes the reaction was completed. Upon completion of the reaction, a rigid foam, suitable as insulative material, was obtained.
• Example 2 The procedure of Example 1 was repeated using 0.5 part of a 2,4,6-tris(diisopropanolamino)-s-triazine catalyst in lieu of the 2,4,6-tris(diethanolamino)-s-triazine catalyst of Example 1. This reaction was conducted over a temperature parameter of about C. to 135 C.
• the exotherm occurred after about 60 minutes and reached a maximum temperature of about 205 C.
• the final product was a rigid foam, characterized by carbodiimide linkages, suitable as insulation and the like.
• EXAMPLES 3-7 Following the procedure of Example 1, a series of carbodiimide foams were prepared by condensing different organic diisocyanates and blends thereof in the presence of 2,4,6-tris(diethanolamino)-s-triazine. These diisocyanates and the amounts thereof, as well as the reaction conditions, are tabulated below in Table I.
• the temperature employed in preparing the foams of this example ranged from about C. to C.
• the catalyst was 2,4,6-tris(diethanolamiuo)-s-triazine.
• the same procedure as outlined in Example 1 was employed, i.c., a mixture of the polyisocyanate, catalyst and other ingredients was charged to a suitable reaction vessel equipped with a magnetic stirrer and seated atop a suitable heating means. The mixture was maintained at a temperature ranging from about 100 C. to 105 C. under agitation until the exotherm occurred.
• the plasticizer consisted of tris(beta-chloroethyl) phosphate.
• EXAMPLE 8 A rigid carbodiimide foam was prepared from the following ingredients.
• a rigid carbodiimide foam was prepared from the following ingredients.
• EXAMPLE 10 A rigid carbodiimide foam was prepared from the following ingredients.
• the resulting foam had a density of 0.83 lb./cu. ft.
• n Prepared from 10/1 parts of TDI and a polypropylene glycol having an average molecular weight of 400. Prepared from 10/1 parts of TDI and a polypropylene glycol having an average molecular weight of 1,000. Prepared from 85/15 parts of TDI and a sucrose polyol prepared by oxypropylating sucrose to an average molecular weight of about 800.
• l MDI methylene diphenyl diisocyanate. s N ,N-diphenylethylene diamine.
• EXAMPLE 28 This example illustrates the excellent flame retardancy and low smoke characteristics of the foams of the present invention.
• a process for the preparation of a rigid cellular foam characterized by carbodiimide linkages which comprises condensing organic polyisocyanate in the presence of a ctalytically suflicient amount of 2,4,6-tris(dialkanolamino) -s-triazine catalyst.
• R is a polyvalent organic radical and z is an integer corresponding to the valence of R and is at least 2.
• R is selected from the group consisting of aliphatic, aromatic, and alkylaryl organic radicals.
• organic polyisocyanate is selected from the group consisting of toluene diisocyanate, crude toluene diisocyanate, crude methylene diphenyl diisocyanate, methylene diphenyl diisocyanate, xylylene diisocyanate, lysine diisocyanate methyl ester, and mixtures thereof.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 1970
  • 1970-01-26 US US5985A patent/US3645923A/en not_active Expired - Lifetime
  • 1970-12-21 GB GB6069870A patent/GB1326240A/en not_active Expired
• 1971
  • 1971-01-20 DE DE2102604A patent/DE2102604B2/de not_active Ceased
  • 1971-01-20 BE BE761775A patent/BE761775A/xx unknown
  • 1971-01-20 NL NL717100779A patent/NL142435B/xx unknown
  • 1971-01-21 FR FR7101982A patent/FR2077618B1/fr not_active Expired

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